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Abstract:

A thin film manufacturing apparatus is disclosed, including a liquid
ejecting unit which ejects a liquid onto an object on which a film is to
be formed and which forms a coating film; a first laser irradiating unit
which continuously irradiates a laser light onto the coating film and
which evaporates a solvent of the coating film; and a second laser
irradiating unit which irradiates a laser light pulse onto the coating
film of which the solvent is evaporated and which crystallizes the
coating film of which the solvent is evaporated.

Claims:

1. A thin film manufacturing apparatus, comprising: a liquid ejecting
unit which ejects a liquid onto an object on which a film is to be formed
and which forms a coating film; a first laser irradiating unit which
continuously irradiates a laser light onto the coating film and which
evaporates a solvent of the coating film; and a second laser irradiating
unit which irradiates a laser light pulse onto the coating film of which
the solvent is evaporated and which crystallizes the coating film of
which the solvent is evaporated.

2. The thin film manufacturing apparatus as claimed in claim 1, further
comprising: a laser power storage unit which calculates in advance and
stores a laser power corresponding to a film thickness of the coating
film based on a relationship between the film thickness and a light
absorption rate of the coating film, wherein the first laser irradiating
unit and the second laser irradiating unit obtains a value of the laser
power corresponding to the film thickness of the coating film, and
irradiates, onto the coating film, the laser light with the laser power
corresponding to the film thickness of the coating film.

3. The thin film manufacturing apparatus as claimed in claim 2, wherein a
wavelength of the laser light irradiated by the respective first laser
irradiating unit and the second laser irradiating unit is at least 400
nm.

4. The thin film manufacturing apparatus as claimed in claim 1, wherein a
shape of a laser light irradiating region on the object on which the film
is to be formed of the second laser irradiating unit is identical to a
shape of the coating film in which the solvent is evaporated.

5. The thin film manufacturing apparatus as claimed in claim 1, wherein a
length in a direction orthogonal to a moving direction of the object on
which the film is to be formed of a laser light irradiating region of the
first laser irradiating unit is identical to a length in a direction
orthogonal to the moving direction of the object on which the film is to
be formed of the coating film.

6. The thin film manufacturing apparatus as claimed in claim 5, wherein a
shape of the coating film is rectangular, and a shape of the laser light
irradiating region on the object on which the film is to be formed of the
first laser irradiating unit or the second laser irradiating unit is
rectangular.

7. The thin film manufacturing apparatus as claimed in claim 6, wherein a
light intensity distribution of the laser light irradiated by the first
laser irradiating unit or the second laser irradiating unit is of a top
hat shape.

8. The thin film manufacturing apparatus as claimed in claim 1, further
comprising: an ultraviolet ray irradiating unit which irradiates
ultraviolet rays onto the coating film of which the solvent is evaporated
and which achieves a chemical bond scission within the metal organic
compound contained in the coating film.

9. A thin film manufacturing method, comprising: forming a
liquid-repellant region and a liquid-philic region on a surface of an
object on which a film is to be formed; ejecting a liquid onto the
liquid-philic region and forming a coating film; irradiating a continuous
laser light onto the coating film and evaporating a solvent of the
coating film; and irradiating a laser light pulse onto the coating film
of which the solvent is evaporated and crystallizing the coating film of
which the solvent is evaporated.

10. The thin film manufacturing method as claimed in claim 9, further
comprising: calculating in advance and storing a laser power
corresponding to a film thickness of the coating film based on a
relationship between the film thickness and a light absorption rate of
the coating film, wherein, in the continuous laser light irradiating and
the laser light pulse irradiating, a value is obtained of the laser power
corresponding to the film thickness of the coating film in the laser
power storing, and the laser light is irradiated, onto the coating film
with the laser power corresponding to the film thickness of the coating
film.

11. A thin film manufacturing apparatus, comprising: a liquid ejecting
unit which ejects a liquid onto an object on which a film is to be formed
and which forms a coating film; an imaging unit which images the coating
film; a color depth converting unit which converts a color of an image
imaged by the imaging unit into a color depth; a film thickness
calculating unit which calculates a film thickness of the coating film
from the color depth; an irradiating power calculating unit which
calculates an irradiating power corresponding to the film thickness
calculated by the film thickness calculating unit; and a laser
irradiating unit which irradiates, onto the coating film, a laser light
with the irradiating power calculated by the irradiating power
calculating unit.

12. The thin film manufacturing apparatus as claimed in claim 11, wherein
the laser irradiating unit irradiates a pulse-shaped laser light onto the
coating film, and heats and crystallizes the coating film.

13. The thin film manufacturing apparatus as claimed in claim 11, further
comprising a continuous laser irradiating unit which continuously
irradiates, onto the coating film, the laser light with the irradiating
power calculated by the irradiating power calculating unit and which
thermally decomposes the coating film.

14. The thin film manufacturing apparatus as claimed in claim 11, further
comprising a shape determining unit which recognizes a shape of the
coating film based on the image imaged by the imaging unit and determines
whether the shape is normal.

15. A thin film manufacturing method, comprising: a region forming step
of forming a liquid-repellant region and a liquid-philic region on a
surface of an object on which a film is to be formed; a coating film
forming step of ejecting a liquid onto the liquid-philic region and
forming a coating film; an imaging step of imaging the coating film; a
color depth converting step of converting a color of an image imaged in
the imaging step into a color depth; a film thickness calculating step of
calculating a film thickness of the coating film from the color depth; an
irradiating power calculating step of calculating an irradiating power
corresponding to the film thickness calculated in the film thickness
calculating step; and a laser irradiating step of irradiating, onto the
coating film, a laser light with the irradiating power calculated in the
irradiating power calculating step.

[0002] A liquid ejecting head and inkjet recording apparatus for use as an
image recording apparatus or an image forming apparatus such as a
printer, a facsimile machine, a copying machine, etc., are known that
include a nozzle which ejects ink droplets; a pressure chamber with which
the nozzle is communicatively connected; and an electro-mechanical
transducer element such as a piezoelectric element which pressurizes ink
within the pressure chamber.

[0003] The electro-mechanical transducer element includes a structure in
which an electro-mechanical transducer film and an upper electrode are
laminated on a lower electrode, for example. The electro-mechanical
transducer film, which is a thin film, may be manufactured by a
sputtering method, an MOCVD method, a vacuum deposition method, an ion
plating method, a sol-gel method, an aerosol deposition method, etc., for
example.

[0004] Here, a manufacturing method of the electro-mechanical transducer
film using the sol-gel method is described as an example. First, a
hydrophobic film pattern is formed on the lower electrode (process 1). A
portion on the lower electrode on which the hydrophobic film pattern is
not formed is hydrophilic. Next, only on the hydrophilic portion (the
portion on which the hydrophobic film pattern is not formed) on the lower
electrode a precursor coating film of the electro-mechanical transducer
film is formed and a thermal treatment is performed (process 2). With the
thermal treatment, the hydrophobic film pattern disappears.

[0005] The precursor coating film of the electro-mechanical transducer
film is thin, so that it is not possible to form it in a predetermined
film thickness in a one time treatment. Thus, processes 1 and 2 are
repeated a required number of times to laminate the precursor coating
film of the electro-mechanical transducer film and manufacture the
electro-mechanical transducer film of a predetermined film thickness.

[0006] However, with the method of manufacturing the electro-mechanical
transducer film as described above, the processes 1 and 2 are repeated a
required number of times, so that the film thickness of the precursor
coating film on which the thermal treatment is to be performed becomes
different every time (the larger the number of times of repetition, the
larger the film thickness becomes). Therefore, there is a problem that,
even when the thermal treatment is performed under the same conditions in
the process 2, it is not possible to heat to the same temperature due to
a difference in a light absorption rate caused by a difference in the
film thickness of the precursor coating film.

[0009] In light of the problem as described above, an object of
embodiments of the present invention is to provide a thin film
manufacturing apparatus and a thin film manufacturing method which make
it possible to perform a preferable heating treatment in accordance with
a film thickness of a thin film to be heated.

[0010] According to an embodiment of the present invention, thin film
manufacturing apparatus is provided, including a liquid ejecting unit
which ejects a liquid onto an object on which a film is to be formed and
which forms a coating film; a first laser irradiating unit which
continuously irradiates a laser light onto the coating film and which
evaporates a solvent of the coating film; and a second laser irradiating
unit which irradiates a laser light pulse onto the coating film of which
the solvent is evaporated and which crystallizes the coating film of
which the solvent is evaporated.

[0011] Embodiments of the present invention make it possible to provide a
thin film manufacturing apparatus and a thin film manufacturing method
that make it possible to perform a preferable heating treatment in
accordance with a film thickness of a thin film to be heated.

BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Other objects, features, and advantages of the present invention
will become more apparent from the following detailed descriptions when
read in conjunction with the accompanying drawings, in which:

[0013] FIG. 1 is a first part of a sectional view exemplifying a liquid
ejecting head which uses an electro-mechanical transducer element;

[0014] FIG. 2 is a second part of the sectional view exemplifying the
liquid ejecting head which uses the electro-mechanical transducer
element;

[0015] FIG. 3 is a perspective view exemplifying a thin film manufacturing
apparatus according to a first embodiment;

[0016] FIGS. 4A to 4D are first parts of a diagram exemplifying a thin
film manufacturing process according to the present embodiment;

[0017] FIGS. 5A to 5C are second parts of the diagram exemplifying the
thin film manufacturing process according to the present embodiment;

[0018] FIGS. 6A and 6B are third parts of the diagram exemplifying the
thin film manufacturing process according to the present embodiment;

[0019] FIGS. 7A to 7D are fourth parts of the diagram exemplifying the
thin film manufacturing process according to the present embodiment;

[0020] FIG. 8 is a diagram illustrating a relationship between a color
depth and a film thickness;

[0021] FIG. 9 is a diagram for explaining a light absorption rate and the
film thickness;

[0022] FIG. 10A is a diagram illustrating an example of a flowchart for
measuring a relationship between the light absorption rate and the film
thickness of a functional ink and FIG. 10B is a diagram illustrating an
example of information obtained in step S102 in FIG. 10A;

[0023] FIG. 11 is a diagram illustrating a functional ink pattern
recognized by a camera;

[0024] FIG. 12A is a diagram illustrating an example of information
obtained in step S103 in FIG. 10A, and FIG. 12B is a diagram in which
film thickness information obtained in FIG. 10B is plotted in FIG. 12A;

[0026] FIG. 14 is a side view exemplifying a machinery section of the
inkjet recording apparatus;

[0027] FIG. 15 is a photograph in which a water contact angle is measured
in an SAM film forming part;

[0028] FIG. 16 is a photograph in which the water contact angle is
measured in an SAM film removing part; and

[0029] FIG. 17 is graph showing a P-E hysteresis curve of the
electro-mechanical transducer element manufactured in examples of the
present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

[0030] A description is given below with regard to embodiments of the
present invention with reference to the drawings. In the respective
drawings, the same letters are applied to the same elements, so that
duplicate explanations may be omitted.

First Embodiment

Thin Film

[0031] First, an electro-mechanical transducer film which makes up an
electro-mechanical transducer element is described as an example of a
thin film which is manufactured by a thin film manufacturing method and a
thin film manufacturing apparatus according to a first embodiment. It is
a matter of course that the thin film which can be manufactured by the
thin film manufacturing method and the thin film manufacturing apparatus
according to the first embodiment is not limited to the
electro-mechanical transducer film.

[0032] The electro-mechanical transducer element is used as a component of
a liquid ejecting head used in an inkjet recording apparatus, for
example. FIG. 1 is a sectional view exemplifying the liquid ejecting head
which uses the electro-mechanical transducer element.

[0033] With reference to FIG. 1, a liquid droplet ejecting head 1 includes
a nozzle plate 10; a pressure chamber substrate 20; a vibrating plate 30;
and an electro-mechanical transducer element 40. A nozzle 11 which ejects
ink droplets is formed in the nozzle plate 10. The nozzle plate 10, the
pressure chamber substrate 20, and the vibrating plate 30 form a pressure
chamber 21 (may also be called an ink flow path, a pressurizing liquid
chamber, a pressurizing chamber, an ejecting chamber, a liquid chamber,
etc.), which is communicatively connected to the nozzle 11. The vibrating
plate 30 forms a part of a wall face of the ink flow path.

[0034] The electro-mechanical transducer element 40, which is configured
to include a contact layer 41, a lower electrode 42, an
electro-mechanical transducer film 43, and an upper electrode 44,
includes a function of pressurizing ink within the pressurizing chamber
21. The contact layer 41, which is a layer including Ti, TiO2, TiN,
Ta, Ta2O5, Ta3N5, etc., for example, includes a
function of improving adhesion between the lower electrode 42 and the
vibrating plate 30. However, the contact layer 41 is not a mandatory
element of the electro-mechanical transducer element 40.

[0035] When a voltage is applied between the lower electrode 42 and the
upper electrode 44 in the electro-mechanical transducer element 40, the
electro-mechanical transducer film 43 is mechanically displaced. With the
mechanical displacement of the electro-mechanical transducer film 43, the
vibrating plate 30 is deformed and displaced in a lateral direction (a
d31 direction), for example, pressurizing the ink within the pressure
chamber 21. This makes it possible to cause ink droplets to be ejected
from the nozzle 11.

[0036] As shown in FIG. 2, multiple of the liquid droplet ejecting heads 1
may also be installed together to configure a liquid droplet ejecting
head 2.

[0037] As a material for the electro-mechanical transducer film 43, PZT
may be used, for example. PZT is a solid solution of lead zirconate
(PbZrO3) and lead titanate (PbTiO3). For example, a PZT, etc.,
may be used at a ratio between PbZrO3 and PbTiO3 of 53:47,
which is expressed in a chemical formula as Pb(Zr0.53,
Ti0.47)O3 and generally denoted as PZT (53/47). The properties
of PZT vary depending on the ratio between PbZrO3 and PbTiO3.

[0038] When using PZT for the electro-mechanical transducer film 43, a
lead acetate, a zirconium alkoxide compound, and a titanium alkoxide
compound, which are used as starting materials, are dissolved in
methoxyethanol as a common solvent to produce a PZT precursor solution. A
skilled person may appropriately select an amount of mixture of the lead
acetate, the zirconium alkoxide compound, and the titanium alkoxide
compound in accordance with a desired PZT composition the ratio between
PbZrO3 and PbTiO3).

[0039] A metal alkoxide compound is easily hydrolyzed by moisture in the
atmosphere. Therefore, a stabilizer, such as acetylacetone, acetic acid,
diethanolamine, etc., may be added to the PZT precursor solution.

[0040] As the material for the electro-mechanical transducer film 43,
barium titanate, etc., may also be used, for example. In this case, a
barium alkoxide and a titanium alkoxide compound, which are used as
starting materials, can be dissolved in a common solvent to produce a
barium titanate precursor solution.

[0041] Complex oxides with A=Pb, Ba, Sr; B═Ti, Zr, Sn, Ni, Zn, Mg, Nb
as main components apply to such materials described with a general
formula ABO3. A specific description thereof may be
(Pb1-x,Ba)(Zr,Ti)O3, (Pb1-x,Sr)(Zr,Ti)O3, which is a
case in which Pb in site A is partially replaced by Ba and Sr. Such
replacement is possible for a bivalent element, the effect of which is
that an action of reducing characteristic deterioration due to
evaporation of lead during a thermal treatment is demonstrated.

[0042] As a material for the lower electrode 42, a metal, etc., which have
a high heat resistance and which form an SAM film by a reaction with
alkanethiols as shown below, may be used. More specifically, platinum
group metals such as ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium
(Os), iridium (Ir), platinum (Pt), etc., or alloy materials, etc.,
including these platinum group metals may be used.

[0043] Moreover, after producing these metal layers, a conductive oxide
layer may be laminated to use the laminated result. More specifically, as
the conductive oxide, there is a complex oxide, which is described with a
chemical formula ABO3 and which has A=Sr, Ba, Ca, La, B═Ru, Co,
Ni as main components, including SrRuO3, CaRuO3;
(Sr1-xCax)O3, which is a solid solution thereof; as well
as LaNiO3, SrCoO3, and (La,Sr)(Ni1-yCoy)O3 (may
be y=1), which is a solid solution thereof. Other oxide materials also
include IrO2, RuO2.

[0044] The lower electrode 42 may be produced by methods such as a vacuum
film forming method, etc., including vapor deposition, sputtering, etc.,
for example. The lower electrode 42 is used for an electrical connection
as a common electrode for inputting a signal into the electro-mechanical
transducer element 40, so that, for a vibrating plate 30 thereunder, an
insulator, or a conductor whose surface is insulated may be used.

[0045] As a specific material for the vibrating plate 30, silicon may be
used, for example. Moreover, as a specific material for insulating the
surface of the vibrating plate 30, a silicon oxide film, a silicon
nitride film, or a silicon oxynitride film of a thickness of
approximately a few hundred nm to a few μm, a film in which these
films are laminated, etc., may be used. Moreover, taking into account a
thermal expansion difference, a ceramic film such as an aluminum oxide
film, a Zirconia film, etc., may be used. A silicon-based insulating film
which insulates the surface of the vibrating plate 30 may be formed by a
thermal oxidation treatment of silicon, a CVD method, etc. Moreover, a
metal oxide film such as an aluminum oxide film, etc., which insulates
the surface of the vibrating plate 30 may be formed by sputtering, etc.

[0046] Thin Film Manufacturing Apparatus

[0047] Next, a structure of a thin film manufacturing apparatus according
to the first embodiment is described. FIG. 3 is a perspective view
exemplifying a thin film manufacturing apparatus according to the first
embodiment. With reference to FIG. 3, a Y-axis drive unit 61 is installed
on a platform 60 in the thin film manufacturing apparatus 3. On the
Y-axis drive unit 61 is installed a stage 62 which has installed thereon
a substrate 5 such that the stage 62 can drive in a Y-axis direction.

[0048] The stage 62 normally accompanies an adsorbing unit (not shown)
which uses a vacuum, static electricity, etc., by which adsorbing unit
the substrate 53 may be fixed. Moreover, also have the stage 62 installed
thereon a drive unit (not shown) which rotates around a Z axis to correct
a tilt of an inkjet head 67, a continuous laser irradiating apparatus 71,
and a pulse laser irradiating apparatus 72, and an gin unit 73 that are
described below, relative to the substrate 5.

[0049] Moreover, an X-axis supporting member 64 for supporting an X-axis
drive unit 63 is installed on the platform 60. On the X-axis drive unit
63 is installed a Z-axis drive unit 65, on which is mounted a head base
66, which is arranged to move in X-axis and Z-axis directions.

[0050] The Z-axis drive unit 65 may control a distance between the
substrate 5 and the inkjet head 67 described below. On the head base 66
is installed the inkjet head 67 which ejects a functional ink (a PZT
precursor solution, for example). To the inkjet head 67 is provided a
functional ink via an ink-supplying pipe (not shown) from each ink tank
68.

[0051] On the X-axis drive unit 63 is mounted a different Z-axis drive
unit 69, on which Z-axis drive unit 69 a laser support member 70 is
mounted. On the laser support member 70 may be mounted the continuous
laser irradiating apparatus 71 and the pulse laser irradiating apparatus
72 as well as the imaging apparatus 73. The z-axis drive unit 69 may
drive a distance between the substrate 5, and the continuous laser
irradiating apparatus 71, the pulse laser irradiating apparatus 72 and
the imaging apparatus 73. As the imaging unit 73, a CCD camera, etc., may
be used.

[0052] While FIG. 3 shows a configuration in which the stage 1 has a
degree of freedom of one axis in a Y direction and the inkjet head 67,
the continuous laser irradiating apparatus 71, the pulse laser
irradiating apparatus 72, and the imaging unit 73 has a degree of freedom
of one axis in an X direction, it is not limited thereto. For example,
the stage 62 may be configured to have a degree of freedom of two axes in
the X and Y directions and fix the inkjet head 67, the continuous laser
irradiating apparatus 71, the pulse laser irradiating apparatus 72, and
the imaging unit 73. Moreover, the stage 62 may be configured to have a
degree of freedom of one axis in the Y direction and align the inkjet
head 67, the continuous laser irradiating apparatus 71, the pulse laser
irradiating apparatus 72, and the imaging unit 73 in the Y-axis
direction.

[0053] Moreover, it may be configured to fix the substrate 5, and, for the
inkjet head 67, the continuous laser irradiating apparatus 71, the pulse
laser irradiating apparatus 72, and the imaging unit 73 to have a degree
of freedom of two axes in the X and Y directions. Furthermore, it is not
necessary for the X axis and the Y axis to be orthogonal as long as one
plane may be expressed with X-axis and Y-axis vectors, so that the X-axis
vector may have an angle of 30, 45, or 60 degrees formed with the Y-axis
vector.

[0054] The thin film manufacturing apparatus 3, which has an apparatus
control unit (not shown), may control ejection conditions of the
functional ink of the inkjet head 67 and laser irradiating conditions of
the continuous laser irradiating apparatus 71 and the pulse laser
irradiating apparatus 72.

[0055] An apparatus control unit includes a CPU, a ROM, a RAM, a
non-volatile memory, a main memory, etc., for example, various functions
of which apparatus control unit are realized by a control program
recorded in the ROM, etc., by a control program recorded in the ROM,
etc., being read into the main memory to be executed by the CPU. A part
or the whole of the apparatus control unit may be realized by hardware
only.

[0056] Moreover, the apparatus control unit may physically be configured
by multiple apparatuses. In a recording unit such as the RAM, the
non-volatile memory, etc., may be recorded a crystalline state of the
functional ink and optimal laser irradiating conditions, etc. For
example, a laser power storage unit, a color depth converting unit, a
film thickness calculating unit, an irradiating power calculating unit, a
shape determining unit, etc., according to the present embodiment can be
realized with an apparatus control unit.

[0057] Thin Film Manufacturing Method

[0058] Next, a thin film manufacturing method according to the first
embodiment is described. Here, an example is shown of manufacturing the
electro-mechanical transducer film 43 as the thin film, which is shown in
FIG. 1.

[0059] Patterning of SAM Film

[0060] First, as shown in FIGS. 4A to 4D, a SAM (Self Assembled Monolayer)
film 50 of a predetermined pattern is formed on a surface of the lower
electrode 42. More specifically, in a process shown in FIG. 4A, a
substrate to be the lower electrode 42 is prepared. As the lower
substrate 42, platinum (Pt) may be used, for example.

[0061] Next, in a process shown in FIG. 4B, the lower electrode 42 is
soaking treated with a SAM material including alkanethiols, etc. In this
way, on a surface of the lower electrode 42 the SAM material reacts, so
that the SAM film 50 is affixed thereto, making it possible to make the
surface of the lower electrode 42 water repellent. Alkanethiols, which
vary in reactability and hydrophobicity (water repellency) depending on a
molecular chain length, are normally produced by dissolving a molecule
with the number of carbon atoms between 6 and 18 in an organic solvent
such as alcohol, acetone, toluene, etc. Normally, a concentration of
alkanethiols is approximately a few mols/liter. After a predetermined
time period, the lower electrode 42 is taken out, excessive molecules
undergo replacement cleaning by the solvent and drying.

[0062] Next, in a process shown in FIG. 4C, using a known
photolithographic method, a photoresist 51 having an opening 51x is
formed on the SAM film 50 which is formed on the surface of the lower
electrode 42. Then, in a process shown in FIG. 4D, using dry etching,
etc., the SAM film 50 which is exposed within the opening 51x is removed,
and furthermore the photoresist 51 is removed. In this way, the SAM film
50 of a predetermined pattern is formed on a surface of the lower
electrode 42.

[0063] A region on which the SAM film 50 is formed on a surface of the
lower electrode becomes hydrophobic. On the other hand, a region on which
the SAM film 50 is removed so that the surface of the lower electrode 42
is exposed becomes hydrophilic. A contrast of the surface energy can be
used to coat the PZT precursor solution differently as described in
detail below.

[0064] After the process shown in FIG. 4A, as in a process shown in FIG.
5A, a photoresist 53 may be formed on the surface of the lower electrode
42, an SAM treatment may be performed as in a process shown in FIG. 5B,
and the photoresist 53 may be removed as in the process shown in FIG. 5C.
In this way, in the same manner as the process shown in FIG. 4D, the SAM
film 50 of a predetermined pattern is formed on the surface of the lower
electrode 42.

[0065] Moreover, after the process shown in FIG. 4B, as in a process shown
in FIG. 6A, ultraviolet rays, oxygen plasma, etc., may be irradiated onto
the surface of the lower electrode 42 via a photomask 54 having an
opening 54x as in a process shown in FIG. 6A and the SAM film 50 of an
exposing portion (within the opening 54x) may be removed as shown in a
process shown in FIG. 6B. In this way, in the same manner as the process
shown in FIG. 4D, an SAM film 50 of a predetermined pattern is formed on
the surface of the lower electrode 42.

[0066] Forming Electro-Mechanical Transducer Film

[0067] Next, as shown in FIGS. 7A to 7D, an electro-mechanical transducer
film 43 is formed on the surface of the lower electrode 42. More
specifically, in the process shown in FIG. 7A, the lower electrode 42
(corresponding to the substrate 5 in FIG. 3) on which surface the SAM
film 50 of a predetermined pattern is formed is placed on the stage 62 of
the thin film manufacturing apparatus 3. Then, using a well known
alignment apparatus (a CCD camera, a CMOS camera, etc.), etc., a
position, tilt, etc., of the lower electrode 42 is aligned.

[0068] Then, the inkjet head 67 is driven to the X axis and the stage 62
on which the lower electrode 42 is placed is driven to the Y axis, so
that the inkjet head 67 is arranged on the stage 62. Then, a functional
ink 43a is ejected from the inkjet head 67 onto a region (a hydrophilic
region) on which there is no SAM film 50 on the surface of the lower
electrode 42. Here, due to a contrast of the surface energy, the
functional ink 43a undergoes wet spreading only onto a region on which
there is no SAM film 50 (a hydrophilic region).

[0069] In this way, a contrast of the surface energy can be used to form a
functional ink 43a only onto a region on which there is no SAM film 50 (a
hydrophilic region) to decrease an amount of use of a solution for
coating relative to a process such as spin coating, etc., and simplify
the process. As the functional ink 43a, a PZT precursor solution may be
used, for example.

[0070] Next, in the process shown in FIG. 7B, a continuous laser
irradiating apparatus 71 is driven to the X axis and, as needed, a stage
62 on which the lower electrode 42 is placed is driven to the Y axis to
arrange the continuous laser irradiating apparatus 71 on the stage 62.
Then, in the continuous laser irradiating apparatus 71, the functional
ink 43a which underwent wet spreading in the process shown in FIG. 7A
undergoes irradiation of the laser light 71x and heating. The functional
ink 43a on which the laser light 71x is irradiated, a solvent of which
evaporates, is thermally decomposed, and becomes a functional ink 43b
which is thermally decomposed. As the continuous laser irradiating
apparatus 71, a semiconductor laser apparatus, a YAG laser apparatus,
etc., may be used, for example.

[0071] A wavelength of the laser light 71x is preferably set to be greater
than or equal to 400 nm (for example, in the order of between 400 nm to
10000 nm), which is a region in which a light absorption rate of the
substrate including the lower electrode 42 is relatively high. Explaining
in more detail, the functional ink 43a almost transmits and poorly
absorbs the laser light 71x whose wavelength is greater than or equal to
400 nm. Therefore, the functional ink 43a is not directly heated, while a
substrate which includes the lower electrode 42 (platinum, etc.) which
has mounted thereon the functional ink 43a is heated, and in conjunction
therewith the functional ink 43a is indirectly heated. Therefore, the
wavelength of the laser light 71x is preferably set to be greater than or
equal to 400 nm, in which a light absorption rate of the lower electrode
42 is relatively high.

[0072] While unevenness of a beam profile of the laser light could cause
temperature unevenness in the irradiating portion to occur when a direct
heating method is used, an indirect heating method can be adopted to heat
the functional ink 43a uniformly within the irradiating face.

[0073] Moreover, while the functional ink 43a is formed on the lower
electrode 42 in the above explanation, the lower electrode 42 which
includes platinum, etc., and the contact layer 41 which includes
titanium, etc., may be laminated on the vibrating plate 30 made of
silicon, forming the functional ink 43a on the laminated lower electrode
42. Even in this case, the wavelength of the laser light 71x is
preferably set to be greater than or equal to 400 nm, in which region a
light absorption rate of silicon, titanium, and platinum is relatively
high.

[0074] Silicon, which has low unevenness of thickness and crystallization
and thermal properties within a face, has a high reliability, so that it
is suitable for a substrate (the vibrating plate 30) which is used in the
present embodiment.

[0075] A moving speed of the lower electrode 42 may be set to be
approximately 10 mm/s to 1000 mm/s, while a power of the laser light 71x
may be set to be approximately a few W to a few ten W. Moreover, a beam
diameter of the laser light 71x may be set to be in the order of a few
ten μm to a few hundred μm, while the beam profile may be set to be
a general Gaussian profile.

[0076] The laser light 71x is also irradiated onto the SAM film 50, so
that the SAM film 50 is also heated. While the SAM film 50 could
disappear when it reaches a temperature of greater than or equal to
500° C., a temperature of the lower electrode 42 remains at less
than or equal to 500° C., so that the SAM film 50 does not
disappear.

[0077] Next, in the process shown in FIG. 7C, the imaging unit 73 is
driven to the X axis and, as needed, the stage 62 on which the lower
electrode 42 is placed is driven to the Y axis to arrange the imaging
unit 73 on the stage 62. Then, in the imaging unit 73, a pattern of the
functional ink 43 which was thermally decomposed in the process shown in
FIG. 7B is imaged. The imaging unit 73 is preferably arranged such that
the whole area of the functional ink 43b can be imaged at once.

[0078] A pattern image of the functional ink 43b that is imaged by the
imaging unit 73 is taken into an apparatus control unit (not shown) of
the thin film manufacturing apparatus, and colors of the pattern is
converted into a color depth. The colors of the pattern may be converted
into the color depth of 256 gradations for each of R, G, and B, for
example.

[0079] While a relationship between the color depth and the film thickness
changes in accordance with a range of the film thickness, as shown in
FIG. 8, the relationship between the color depth and the film thickness
for red (R) becomes almost linear for the film thickness of 2 μm as in
the present embodiment. Therefore, using this relationship, a film
thickness may be determined from the color depth. While the relationship
between the color depth and the film thickness for red (R) is used in the
present embodiment, the relationship between the color depth and the film
thickness for green (G) or blue (B) may be used. It is preferable to
determine the film thickness from the color depth for the color for which
the relationship between the color depth and the film thickness is more
linear.

[0080] Moreover, as shown in FIG. 12A, the light absorption rate of a
laser light changes in accordance with the film thickness. FIG. 12A plots
the light absorption rate when a light with a wavelength of approximately
1000 nm is irradiated. In FIG. 12A, a solid line represents a light
absorption rate for a film thickness of the functional ink film of
between 0 and 1000 μm when burned at 120° C. for a few minutes
with the hot plate; a rough dotted line represents a light absorption
rate for a film thickness of the functional ink film of between 0 and
1000 μm when burned at 500° C. for a few minutes with the oven;
and a fine dotted line represents a light absorption rate for a film
thickness of the functional ink film of between 0 and 1000 μm when
burned at 700° C. for a few minutes with the oven.

[0081] With actual data being measured in a few tens of micrometers, FIG.
12A shows curve-fitted results. Spin coat film forming conditions or
inkjet ejecting conditions can be changed to change a film thickness in
increments of a few ten μm. While temperatures for measurement in the
present embodiment are 120° C., 500° C., and 700°
C., it is a matter of course that more accurate information is obtained
by obtaining data up to 25° C. or data in finer temperature
increments.

[0082] A film thickness of a functional ink film may be measured using a
non-contact shape measuring machine, etc., using a light, etc. for
example. More specifically, an interferometer New View series by Zygo
Corporation, a laser shape-measuring laser microscope VK series by
Keyence Corporation, etc., may be used, for example. The light absorption
rate may be measured using FTIR, UV-VIS-NIR Spectrometry, etc., for
example. More specifically, IR series and UV series by Shimadzu
Corporation, Lambda series by Perkin Elmer, Inc., etc., may be used, for
example.

[0083] Based on the relationships in FIGS. 8 and 12A, a light absorption
rate of the functional ink 43b may be determined from the color depth of
the pattern image of the functional ink 43b. Moreover, when the light
absorption rate is determined, an optimal laser power in accordance with
the light absorption rate may be calculated, so that, after all, an
optimal laser power to be irradiated onto the functional ink 43b of the
film thickness may be determined from the color depth of the pattern
image of the functional ink 43b.

[0084] In order to determine an optimal laser power, first, an optimal
laser power to be used as a reference is determined by prior evaluation.
For example, suppose an optimal laser power for heating the functional
ink 43b of the film thickness 100 nm to 700° C. is 100 W. From
FIG. 12A, the light absorption rate in this case is approximately 36%.

[0085] With this as a reference, an optimal laser power for different film
thicknesses may be determined. For example, from FIG. 12A, the light
absorption rate of the functional ink 43b of the film thickness 200 nm is
approximately 82%. Therefore, 36%/82% of 100 W, or approximately 44 W is
an optimal laser power for heating the functional ink 43b of the film
thickness of 200 nm to 700° C.

[0086] Then, the relationship between the optimal laser power and the
color depth of the pattern image of the functional ink 43b is stored in
advance as data in a non-volatile memory, a RAM of the apparatus control
unit (not shown). In this way, in the process shown in FIG. 7C, the
apparatus control unit may determine an optimal laser power to be
irradiated onto the functional ink 43b from a pattern image of the
functional ink 43b that is imaged by the imaging unit 73.

[0087] Next, in the process shown in FIG. 7D, a pulse laser irradiating
apparatus 72 is driven to the X axis and, as needed, the stage 62 on
which the lower electrode 42 is placed is driven to the Y axis to arrange
the pulse laser irradiating apparatus 72 on the stage 62. Then, in the
pulse laser irradiating apparatus 72, the laser light 72x is irradiated
onto and heats only the functional ink 43b which is decomposed in the
process shown in FIG. 7B. In other words, when the laser light 72x is
irradiated onto the SAM film 50, as the temperature of the lower
electrode 42 reaches 500° C. or above, the SAM film 50 could
disappear, so that the laser light 72x is not irradiated onto the SAM
film 50.

[0088] The functional ink 43b, onto which the laser light 72x is
irradiated, crystallizes to become a functional ink 43c (a PIT thin film,
for example), so that the SAM film 50 remains, without disappearing. As
the pulse irradiating laser apparatus 72, a semiconductor fiber coupling
laser apparatus, a semiconductor laser stack apparatus may be used, for
example.

[0089] A power of the laser light 72x to be irradiated in this process is
an optimal power determined in the process shown in FIG. 7C. A
temperature needed for crystallizing the functional ink 43b is
approximately 700° C., so that an optimal power is irradiated
which is determined using the data of 700° C. in FIG. 12A. Power
of the laser light 72x may be set to approximately a few W to a few ten
W.

[0090] An irradiating time of the laser light 72x may be set to
approximately a few μm to a few hundred μm. A light emitting
frequency of the laser light 72x is preferably adjusted in accordance
with a pattern of the functional ink 43b and a moving speed of the stage
62. For example, when a pattern interval is 100 μm and a moving speed
of the stage 62 is 100 mm/s, the light emitting frequency of the laser
light 72x may be set to 1 kHz.

[0091] When the stage 62 moves while the laser light 72x is emitting
light, a range of irradiating the laser light 72x becomes wider. For
example, when the irradiating time is 100 μm and the moving speed of
the stage 62 is 100 mm/s, the stage 62 moves when the laser light 72x
emits light, so that a range of irradiating the laser light 72x becomes
wider by approximately 10 μm.

[0092] Therefore, in order to irradiate the laser light 72x onto only the
functional ink 43b and not onto the SAM film 50, it is necessary to emit
the laser light 72x at an irradiation timing which matches a pattern
shape of the functional ink 43b, taking into account an irradiating range
of the laser light 72x.

[0093] While a multi-channel one or a one with a singular port may be used
for the pulse laser irradiating apparatus 72, it is preferable to use the
multi-channel one. This is because, as shown in a below-described example
in FIG. 11, a laser light may be irradiated onto each pattern at a
stretch when multiple patterns are installed together.

[0094] A film thickness of the functional ink 43c (for example, a PZT thin
film) which is crystallized in the process shown in FIG. 7D is
approximately a few tens of nanometers. The film thickness is inadequate,
so that after the process shown in FIG. 7D, processes shown in FIGS. 7A
to 7D may be repeated a required number of times. In this way, the
functional ink 43c is laminated, and a crystallized functional ink film,
or in other words the electro-mechanical transducer film 43 is produced
on the lower electrode 42 with an arbitrary pattern and thickness
(approximately a few μm, for example).

[0095] Here, while the film thickness of the functional ink 43c changes
(increases) each time each process is repeated, an optimal laser power to
be irradiated onto the functional ink 43b is determined each time from a
pattern image of the functional ink 43b that is imaged by the imaging
unit 73 in the process shown in FIG. 7C, an optimal laser power
corresponding to the film thickness of the functional ink 43b may always
be irradiated in the process shown in FIG. 7D.

[0096] In this way, in the first embodiment, at a temperature level such
that the SAM film 50 does not disappear, the functional ink 43a undergoes
irradiation of the laser light 71x and heating by the continuous laser
irradiating apparatus 71, a solvent of the functional ink 43a is
evaporated and thermally decomposed, and the functional ink 43b is
produced. Then, the functional ink 43b undergoes irradiation of the laser
light 72x (pulse) and heating, and is crystallized to produce the
functional ink 43c. In this case, with the pulse laser irradiating
apparatus 72, the laser light 72x is not irradiated onto the SAM film 50,
which does not disappear and thus remains.

[0097] In this way, the functional ink 43c may be laminated by repeating a
required number of times only the processes shown in FIGS. 7A to 7D,
without having to repeat the processes in FIGS. 4A to 6B. In other words,
a thin film such as an electro-mechanical transducer film can be
manufactured by a simple process.

[0098] Now, when the functional ink 43c is laminated, a film thickness
becomes thick, so that a light absorption rate of the functional ink 43c
changes. When the light absorption rate changes, a temperature to heat to
differs even when a laser light of the same power level is irradiated.
Therefore, in the processes shown in FIGS. 7B and 7D, in order to heat
the functional ink 43c to a certain temperature, it is preferable to set
a power level of the laser light to irradiate onto the functional ink 43c
in correspondence with the number of times the functional ink 43c is
laminated. (In other words, it is preferable to set it in correspondence
with the film thickness of the functional ink 43.) A method of setting a
power level of the laser light in correspondence with a film thickness of
the functional ink 43c is described below.

[0099] In the process shown in FIG. 7D, an optimal laser power
corresponding to a film thickness of the functional film 43b may always
be irradiated since an optimal laser power to be irradiated onto the
functional ink 43b is determined each time from a pattern image of the
functional ink 43b that is imaged by the imaging unit 73 in FIG. 7C.

[0100] In the above explanations, a laser light is irradiated with an
optimal laser power only in the process shown in FIG. 70. This is because
a power setting of continuously irradiating laser light may be relatively
rough as the continuously irradiating laser light in the process shown in
FIG. 7B has a large range of tolerance in unevenness relative to the
pulse irradiating laser light in the process shown in FIG. 70.

[0101] However, also in the process shown in FIG. 7B, the laser power may
be optimized by the same method as the process shown in FIG. 70. In this
case, a temperature needed for evaporating a solvent of the functional
ink 43a is approximately 120° C., so that first an optimal power
is irradiated which is determined using data of 120° C. in FIG.
12A. Moreover, a temperature needed for thermally decomposing the
functional ink 43a is approximately 500° C., so that after the
evaporating of the solvent, an optimal power is irradiated which is
determined using data of 500° C. in FIG. 12A.

[0102] FIG. 9 is a diagram for explaining the light absorption rate and
the film thickness. When the functional ink 43a is coated on the lower
electrode 42 and the laser light 71x is irradiated thereonto, a part of
the laser light 71x is reflected on a film surface of the functional ink
43a (A); a part thereof is transmitted through the functional ink 43a to
be reflected on a surface of the lower electrode 42 (B), and a part is
absorbed in the lower electrode 42 (C). A part may also be transmitted
through the lower electrode 42. A light absorption rate of the functional
ink 43a changes with a film thickness H of the functional ink 43a. The
same applies to the functional ink 43b.

[0103] Thus, it is necessary to measure a relationship between the light
absorption rate and the film thickness of the functional ink 43a. FIG.
10A is an example of a flowchart for measuring a relationship between the
light absorption rate and the film thickness of a functional ink. When
the relationship between the light absorption rate and the film thickness
of the functional ink 43a is measured in advance, there is no need to
measure it in a mass production process.

[0104] With reference to FIG. 10A, first in step S101, a functional ink is
uniformly coated onto a substrate to be an object on which a film is
formed by an inkjet method or a spin coating method, for example, to form
a functional ink film.

[0105] Next, in step S102, a film thickness of the functional ink film
formed in step S101 is measured. A film thickness of the functional ink
film may be measured using a non-contact shape measuring machine, etc.,
using a light, etc. for example. More specifically, an interferometer New
View series by Zygo Corporation, a laser shape-measuring microscope VK
series by Keyence Corporation, etc., may be used, for example.

[0106] Next, in step S103, a light absorption rate of the functional ink
film formed in step S101 is measured. The light absorption rate of the
functional ink film may be measured using FTIR, UV-VIS-NIR Spectrometry,
etc., for example. More specifically, IR series and UV series by Shimadzu
Corporation, Lambda series by Perkin Elmer, Inc., etc., may be used, for
example.

[0107] Next, in step S104, a functional ink film formed in step S101 is
heated. In order to heat the functional ink film, an oven, an RTA, etc.,
may be used, for example. Moreover, a laser apparatus may be used.

[0108] Next, while determining whether there is a change in film thickness
in step S105, steps S102-S104 are repeated, adjusting a laser power level
or conditions on heating temperature and changing a phase state of the
functional ink film. When it is determined that there is no change in
film thickness (when YES) in step S106, information on states (the
heating temperature, the laser power), the film thickness and the light
absorption rate of the functional ink film are recorded.

[0109] Next, while determining whether a target film thickness is reached
in step S107, steps S101 to S106 are repeated to perform wet-on-wet
coating of the functional ink until the target film thickness is reached
to continue recording information on the states (the heating temperature,
the laser power), the light absorption rate and the film thickness of the
functional ink film. In this way, a relationship between the light
absorption rate and the film thickness of the functional ink film
(functional ink 43a and 43b) is obtained.

[0110] FIG. 10B, which is a diagram illustrating an example of information
obtained in step S102 in FIG. 10A, shows a relationship between the
heating temperature and the film thickness of the functional ink film. In
FIG. 10B, 601 represents a film thickness (approximately 170 nm) of the
functional ink film when heated at 120° C. for one minute in a hot
plate; 602 represents a film thickness (approximately 115 μm) of the
functional ink film when heated at 300° C. for a few minutes in an
oven; 603 represents a film thickness (approximately 90 nm) of the
functional ink film when heated at 500° C. for a few minutes in
the oven; and 604 represents a film thickness (approximately 75 nm) of
the functional ink film when heated at 700° C. for a few minutes
in the oven. While not shown in the present embodiment, it is a matter of
course that a film thickness of the functional ink film at room
temperature (approximately 25° C.) can be measured.

[0111] FIG. 12A, which is a diagram illustrating an example of information
obtained in step S103 in FIG. 10A, shows a relationship between the film
thickness and the light absorption rate of the functional ink film. FIG.
12A plots the light absorption rate when a light with a wavelength of
approximately 1000 nm is irradiated. In FIG. 12A, a solid line represents
a light absorption rate for a film thickness of the functional ink film
of between 0 and 1000 μm when burned at 120° C. for a few
minutes in the hot plate; a rough dotted line represents a light
absorption rate for a film thickness of the functional ink film of
between 0 and 1000 μm when burned at 500° C. for a few minutes
in the oven; and a fine dotted line represents a light absorption rate
for a film thickness of the functional ink film of between 0 and 1000
μm when burned at 700° C. for a few minutes in the oven.

[0112] With actual data being measured in increments of a few ten μm,
FIG. 12A shows curve-fitted results. Spin coat film forming conditions or
inkjet ejecting conditions can be changed to change a film thickness in
increments of a few μm. While temperature points for measurement in
the present embodiment are three points at 120° C., 500°
C., and 700° C., it is a matter of course that more accurate
information is obtained by obtaining data up to 25° C. or data in
finer temperature increments.

[0113] Next, a method of calculating optimal laser power is described
based on pre-measured results of FIGS. 10B and 12A. FIG. 12B is a diagram
in which film thickness information (film thickness information at the
time of heating from 120° C. to 700° C. that are obtained
in FIG. 10B) obtained in FIG. 10B is plotted in FIG. 12A.

[0114] The film thickness is approximately 170 nm at 120° C. in
FIG. 10B, so that plotting it on a light absorption rate curve (solid
line) when heated at 120° C. in FIG. 12B yields a point denoted by
701. In the same manner as described above, plotting film thickness
information when heated at 500° C. and when heated at 700°
C. yields points denoted by 703 and 704.

[0115] FIG. 12B indicates that, when a light with a wavelength of
approximately 1000 nm is irradiated to heat the functional ink film from
120° C. to 700° C., the light absorption rate changes
non-linearly from approximately 52% to approximately 58% to approximately
46%. Wet-on-wet coating of the functional ink is performed for the second
layer in the same manner as for the first layer (the final film thickness
for the first layer is 75 nm, so that a thickness of the second layer
after heating at 120° C. becomes 75 nm+170 nm=245 nm) and the
light absorption rate and the film thickness are measured to plot in FIG.
12B to yield a point denoted by 801.

[0116] In the same manner as the above, film thickness information sets at
times of heating at 500° C. and at 700° C. (approximately
165 μm at 500° C. and approximately 150 μm at 700°
C.) are plotted on the respective curves to yield points denoted by 803
and 804. The light absorption rate for the second layer changes
differently from that for the first layer in that it changes non-linearly
from approximately 62% to approximately 42% to approximately 38%. In this
way, a characteristic in which the light absorption rate varies
substantially depending on the film thickness.

[0117] While a number of methods is possible for determining an optimal
laser power for the respective layers of the laser apparatus which
irradiates a laser light with a wavelength of approximately 1000 nm,
center values of a light absorption rate change range can be used as one
example. Based on the above-described results, a center value of the
light absorption rate for the first layer is 52%, while a center value of
the light absorption rate for the second layer is 50%. The light
absorption rate for the second layer is slightly lower than that for the
first layer, so that it is necessary to irradiate thereonto with a
stronger laser power.

[0118] In the present embodiment, a film thickness of the respective
layers is set to be constant, so that optimal laser power levels for the
respective layers may be determined in proportion to the first laser
power. For example, the optimal laser power for the first layer of 100 W
(the optimal laser power to be a reference needs to be evaluated in
advance) yields the optical laser power for the second layer of 52%/50%
of 100 W, or 104 W. Similarly, for the second layer and beyond, the
optimal laser power may be calculated easily.

[0119] While a case is explained of heating from 120° C. to
700° C. in a single process, when a heating process is performed
which is divided into three stages of evaporation (120° C.),
thermal decomposition (500° C.), and crystallization (700°
C.), it is not necessary to use the central value of the light absorption
rate of the respective states. For example, when only the evaporation
process is to be performed in the laser apparatus, the light absorption
rate of the first layer at 120° C. is 52% and the light absorption
rate of the second layer at 120° C. is 62%, so that, when the
optimal laser power for the first layer is 100 W (similarly, the optimal
laser power to be a reference needs to be evaluated in advance) the
optimal laser power for the second layer becomes 52%/62% of 100 W, or
approximately 84 W. In a manner similar to this scheme, processes of
thermal decomposition (500° C.) and crystallization (700°
C.) may also be performed.

[0120] The optimal laser power to be the reference needs to be evaluated
in advance. In the present embodiment, for a laser irradiating area of
1000 μm×50 μm, a laser wavelength of 980 nm, a laser beam
profile of top hat (flat), and a substrate scanning speed of 100 mm/s,
the optimal laser power was observed in the vicinity of 20 W to 40 W. For
the functional ink film produced under the above-described conditions,
there were no cracks, crystallization was favorable (checked by an XRD
measurement apparatus, etc.), and piezoelectric element characteristics
measured were also favorable.

[0121] In this way, in the first embodiment, based on the relationship
between the film thickness and the light absorption rate of the coating
film, an optimal laser power which corresponds to a film thickness of the
coating film is calculated in advance, which calculated results are
stored in a storage unit. Then, when continuously irradiating a laser
light onto the coating film to evaporate a solvent of the coating film, a
value of an optimal laser power which corresponds to the film thickness
of the coating film that is stored in the storage unit is obtained and a
laser light is irradiated onto the coating film with the optimal laser
power which corresponds to the film thickness of the coating film.
Moreover, when pulse irradiating a laser light onto a coating film in
which the solvent was evaporated to crystallize the coating film in which
the solvent was evaporated, a value of an optimal laser power which
corresponds to the film thickness of the coating film that is stored in
the storage unit is obtained and a laser light is irradiated onto the
coating film with the optimal laser power which corresponds to the film
thickness of the coating film. In this way, a laser light with a laser
power which is optimal for the coating film may be irradiated even when a
film forming process of the coating film is repeated, so that the film
thickness of the coating film changes. In other words, even when the film
thickness of the coating film changes, the coating film may be heated to
a desired temperature. The film thickness of the coating film may be
known from an ejected amount of liquid, etc., so that it is not necessary
to measure the film thickness of the coating film before irradiating the
laser light.

Second Embodiment

[0122] A shape of the pattern image taken into the imaging unit 73 used in
the first embodiment may be measured. In this way, whether a shape of the
pattern produced is normal may be determined. For example, in FIG. 11,
functional inks 43b1, 43b2, and 43b4 show a normal
pattern, while a functional ink 43b3 shows a failure pattern.

[0123] The normal pattern of the functional ink 43b is stored in advance
as data in the RAM or the non-volatile memory of the apparatus control
unit (not shown). In this way, in the process shown in FIG. 7C, the
apparatus control unit may detect a failure pattern by comparing a
pattern image of the functional ink 43b that is imaged by the imaging
unit 73 with a normal pattern stored in advance.

Third Embodiment

[0124] In the first embodiment, the continuous laser irradiating apparatus
71 and the pulse laser irradiating apparatus 72 were used as separate
apparatuses. In the third embodiment, the continuous laser irradiating
apparatus 71 and the pulse laser irradiating apparatus 72 are arranged as
one laser apparatus unit. More specifically, for example, a pulse laser
irradiating apparatus such as a semiconductor fiber coupling laser
apparatus, a semiconductor laser stack apparatus, etc., may be used to
provide the one laser apparatus unit with functions of the pulse laser
irradiating apparatus and the continuous laser irradiating apparatus.

[0125] In this way, processes of solvent evaporation, thermal
decomposition, and crystallization of the functional ink may be performed
by one laser apparatus unit. Moreover, for example, for a configuration
in which the stage 62 has a degree of freedom of one axis in a Y-axis
direction and the inkjet head 67, the continuous laser irradiating
apparatus 71, and the pulse laser irradiating apparatus 72 are aligned in
a Y-axis direction, the continuous laser irradiating apparatus 71 and the
pulse laser irradiating apparatus 72 may be arranged as the one laser
apparatus unit to shorten a length of a Y-axis direction of the stage
drive unit. Therefore, not only a moving accuracy in a Y-axis direction
improves, but an apparatus becomes compact, making a decreased apparatus
cost possible.

Fourth Embodiment

[0126] Normally, a shape of a laser irradiating area by laser heating is
circular, while a beam profile is Gaussian. In this case, when the
functional ink is irradiated at a circular laser irradiating area, an
actual irradiating time differs between a center region of a circle and
an edge portion of the circle. In other words, the circle center is
irradiated longer, while the circle edge is irradiated shorter. Thus, the
laser irradiating area is preferably arranged to have the same shape as
the functional ink pattern or a shape which is larger than the functional
ink pattern. In this way, the functional ink patterned to a predetermined
shape may be heated uniformly.

[0127] Moreover, a beam profile of a laser irradiation by the continuous
laser irradiating apparatus 71 and the pulse laser irradiating apparatus
72 can be arranged as a flat shape or a top hat shape within an
irradiating area to more uniformly heat the functional ink. Adjustment of
the beam profile and the shape of the irradiating area can be
incorporated into either one of the continuous laser irradiating
apparatus 71 and the pulse laser irradiating apparatus 72.

[0128] For example, when a plane shape of the functional ink is
rectangular, for either one of the continuous laser irradiating apparatus
71 and the pulse laser irradiating apparatus 72, the irradiating area is
preferably rectangular when a direction in which the stage 62 may
simultaneously move is one direction. Then, a tilt of the rectangle and a
tilt in a moving direction of the stage 62 are preferably aligned. In
other words, a long side or a short side of the functional ink whose
plane shape is rectangular is preferably parallel to the moving direction
of the stage 62.

[0129] With such a configuration, the irradiating time in the moving
direction of the stage 62 becomes the same in the moving direction and a
direction orthogonal thereto of the stage 62. In other words, a uniform
laser heating becomes possible, making it possible to form a highly
reliable functional ink film.

Fifth Embodiment

[0130] In a fifth embodiment, an excimer laser is used to perform laser
irradiation before performing laser heating for crystallizing functional
ink. A metal organic compound including a metal component is decomposed
at a temperature which varies depending on the metal component included,
so that a method of forming a crystal grain differs depending on the
material. Therefore, the excimer laser is used to perform laser
irradiation to achieve scission of a chemical bond and integrate a method
of forming the crystal grain.

[0131] In this way, when a piezoelectric element is produced from the
functional ink, a crystal film which is compact and which has equal grain
diameters may be formed, so that piezoelectric element characteristics of
the crystal film obtained improves. The chemical bond scission achieved
by the excimer laser may be checked using an infrared absorption
spectrum, etc. More specifically, after the solvent is evaporated by the
continuous laser irradiating apparatus 71, an excimer laser, etc., with a
wavelength of less than or equal to 300 nm is irradiated, for example.

[0132] More specifically, using a continuous irradiation-type KrF excimer
laser apparatus, an excimer laser may be irradiated under irradiating
conditions of a wavelength of between 230 to 280 nm and at least 100
mJ/cm2 to improve the characteristics of functional ink film
obtained. The same advantageous effect is achieved by irradiating
ultraviolet rays using a UV lamp instead of the continuous
irradiation-type KrF excimer laser apparatus.

Sixth Embodiment

[0133] A sixth embodiment shows an example of an inkjet recording
apparatus which has mounted thereon the liquid ejecting head 2 (see FIG.
2) which is manufactured by the thin film manufacturing apparatus 3. FIG.
13 is a perspective view exemplifying an inkjet recording apparatus. FIG.
14 is a side view exemplifying a machinery section of the inkjet
recording apparatus.

[0134] With reference to FIGS. 13 and 14, an inkjet recording apparatus 4
includes, within a recording apparatus body 81 thereof, a printing
machinery unit 82, etc., including a carriage 93 which is movable in a
main scanning direction, an inkjet recording head 94, which is one
embodiment of the liquid droplet ejecting head 2 mounted on the carriage
93; an ink cartridge 95 which supplies ink to the inkjet recording head
94, etc.

[0135] At a lower part of the recording apparatus body 81, a paper-feeding
cassette 84 (or may also be a paper feeding tray) on which a large number
of sheets 83 can be stacked may be mounted such that it can be pulled out
or inserted. Moreover, a manual tray 85 for manually feeding the sheet 83
may be opened or put down. Taking in the sheet 83 fed from the
paper-feeding cassette 84 or the manual tray 85, the print machinery unit
82 records required images, after which it conducts sheet discharging
onto the paper-discharging tray 86 mounted on the back face side.

[0136] The printing machinery unit 82 holds the carriage 93 with a primary
guide rod 91 and a secondary guide rod 92, which are guide members
laterally bridging between right and left side plates (not shown) such
that the carriage 93 can slide in the main scanning direction). On the
carriage 93, an inkjet recording head 94 which ejects ink droplets of
respective colors of yellow (Y), cyan (C), magenta (M), and black (Bk)
ink is mounted such that multiple ink ejecting outlets (nozzles) are
aligned in a direction which crosses the main scanning direction and an
ink droplet ejecting direction faces downwards. Moreover, the carriage 93
has replaceably mounted ink cartridge 95 for supplying ink of each color
to the inkjet recording head 94.

[0137] The ink cartridge 95 has an atmospheric opening (not shown) which
is communicatively connected to the atmosphere at an upper portion
thereof, a supply port (not shown) which supplies ink to the inkjet
recording head 94 at a lower portion thereof, and a porous body (not
shown) which is filled with ink inside thereof. A capillary force of the
porous body keeps ink supplied to the recording head 94 to a slightly
negative pressure. Moreover, while heads of each color are used here as
the inkjet recording head 94, one head may be used which has nozzles
ejecting ink droplets of respective colors.

[0138] The carriage 93 has the downstream side in a sheet conveying
direction thereof slidably fitted to the primary guide rod 91, and has
the upstream side in the sheet conveying direction thereof slidably
placed on the secondary guide rod 92. Then, in order to move and scan
this carriage 93 in the main scanning direction, a timing belt 100 is
stretched between a drive pulley 97 and a follower pulley 98 that are
rotationally driven by the main scanning motor 97, and the carriage 93 is
driven in both ways by rotation of the main scanning motor 97 in normal
and reverse directions. The timing belt 100 is fixed to the carriage 93.

[0139] Moreover, the inkjet recording apparatus 4 is provided with a
friction pad 102, a paper feeding roller 101 which feeds the sheet 83 one
by one from the paper-feeding cassette 84, a guide member 103 which
guides the sheet 83, a conveying roller 104 which reverses the fed sheet
83 to convey the reversed sheet 83, a conveying roller 105 which is
pushed against a peripheral face of the conveying roller 104, and a
leading-end roller 106 which defines an angle of sending out the sheet 83
from the conveying roller 104. In this way, the sheet 83 which is set to
the paper-supplying cassette 84 is conveyed to the lower side of the
inkjet recording head 94. The conveying roller 104 is rotationally driven
via a row of gears by a sub-scanning motor 107.

[0140] A print receiving member 109, which is a sheet guide member,
guides, on the lower side of the recording head 94, the sheet 83 sent out
from the conveying roller 104 in correspondence with a moving range of
the carriage 93 in the main scanning direction. On the downstream side of
the print receiving member 109 in the sheet conveying direction are
provided a spur 112, and a conveying roller 111, which is rotationally
driven to send out the sheet 83 in a discharging direction. Moreover,
there are provided a spur 114, and a discharging roller 113, which sends
out the sheet 83 to the paper-discharging tray 86, and guide members 115
and 116, which form a paper-discharge path.

[0141] At the time of image recording, the inkjet recording head 94 is
driven according to an image signal while moving the carriage 93 to eject
ink onto sheets 83 at rest to record what amounts to one line, and the
following line is recorded after the sheets 83 are conveyed for a
predetermined amount. When a recording termination signal or a signal
that a trailing edge of the sheet 83 has reached the end of the recording
area is received, the recording operation is terminated, so that the
sheets 83 are discharged.

[0142] At a position which is off the recording area on the right end side
in a moving direction of the carriage 93 is provided a recovery apparatus
117 for recovering an ejection failure of the inkjet recording head 94.
The recovery apparatus 117 has a cap unit, an absorption unit, and a
cleaning unit. During the time of waiting for a print, the carriage 93 is
moved to the recovery apparatus 117 side and has the inkjet recording
head 94 capped with a capping unit, preventing an ejection failure due to
drying of ink by maintaining an ejecting outlet in a wet state. Moreover,
ink which is not related to recording is ejected at a time such as in the
middle of recording, making the viscosity of ink at all the ejecting
outlets constant, and maintaining a stable ejection performance.

[0143] When an ejection failure, etc., occurs, the ejecting outlet of the
inkjet recording head 94 is sealed with a capping unit, and air bubbles,
etc., as well as ink are suctioned from the ejecting outlet through a
tube by the suction unit. Moreover, ink, dust, etc., which are adhered to
the ejecting outlet face is removed by a cleaning unit so as to recover
from the ejection failure. Moreover, the suctioned ink is discharged into
a waste ink reservoir (not shown) installed at a lower portion of the
body, and is absorbed and kept by an ink absorber inside the waste ink
reservoir.

[0144] In this way, as the inkjet recording apparatus 4 has mounted
therein an inkjet recording head 94, which is one embodiment of the
liquid ejecting head 2 manufactured by the thin film manufacturing
apparatus 3, it has no ink droplet ejection failure and a stable ink
droplet ejection characteristic is obtained, making it possible to
improve image quality.

Example

[0145] Next, an example is described which forms a thin film using the
thin film manufacturing apparatus 3. In this example, a thermal oxide
film (with a film thickness of 1 μm) is formed on a silicon wafer and,
as a contact layer, a titanium film (with a film thickness of 50 nm) is
formed by sputtering. Then, as a lower electrode, a platinum film (with a
thickness of 200 nm) formed by sputtering.

[0146] Next, the substrate is immersed in a solution of alkanethiol using
CH3(CH2)6--SH at a concentration of 0.01 mol/l (solvent:
isopropyl alcohol), and is subjected to an SAM treatment. Thereafter, the
substrate is, after being washed by isopropyl alcohol and dried,
undergoes a patterning process.

[0147] A water contact angle measured in a SAM film forming part (on the
SAM film) after the SAM treatment was 92.2°. (see FIG. 15) On the
other hand, a water contact angle measured on a platinum-sputtered film
before the SAM treatment was less than equal to 5° (fully wet).
The above described results demonstrate that the SAM film treatment was
performed properly.

[0148] Next, a film was formed by applying a photoresist (TSMR8800)
manufactured by Tokyo Ohka Kogyo Co., Ltd. by a spin coating method, and
a resist pattern has been formed by a conventional photolithography
scheme, after which an oxygen plasma treatment was performed to remove
the SAM film of an exposed portion. A residual resist after the treatment
was dissolved and removed by acetone, and a similar evaluation of the
contact angle as described above was carried out to find that the water
contact angle in the SAM film removing part was less than or equal to
5° (fully wet, see FIG. 16), and that at a part covered with the
resist was 92.4°. It may be confirmed from the above-described
results that patterning of the SAM film was performed properly.

[0149] As a different patterning scheme, a resist pattern was formed in
advance by a similar resist work and a similar SAM film treatment was
carried out, after which the resist was removed by acetone, and a contact
angle was measured. A contact angle on a portion of the platinum film
covered with the resist was less than or equal to 5° (fully wet),
and that at other portions was 92.0° to confirm that the
patterning of the SAM film was performed properly.

[0150] As one further scheme, ultraviolet rays were irradiated using a
shadow mask. More specifically, a vacuum ultrasonic light with a
wavelength of 176 nm by an excimer lamp is used to irradiate for 10
minutes. A contact angle of an irradiating portion was less than or equal
to 5° (fully wet), and that at a non-irradiating portion was
92.2° to confirm that the patterning of the SAM film was performed
properly.

[0151] Next, a film of PZT (53/47) was formed as an electro-mechanical
transducer film. For synthesizing the precursor coating solution, lead
acetate trihydrate, titanium isopropoxide, and zirconium isopropoxide
were used as starting materials. Combined water of lead acetate was
dissolved in methoxyethanol, after which it was dehydrated. An amount of
lead relative to the stoichiometric composition was arranged to be 10 mol
% excess. This is to prevent a decrease in crystallizability due to a
so-called lead falling out in the thermal treatment.

[0152] Titanium isopropoxide and zirconium isopropoxide are dissolved in
methoxyethanol, subjected to an alcohol exchange reaction and an
esterification reaction, and mixed with a methoxyethanol solution in
which is dissolved the above-described lead acetate to synthesize a PZT
precursor solution. The PZT concentration is arranged to be 0.1
mol/liter.

[0153] A film thickness obtained in a one time sol-gel film forming is
preferably 100 nm, and a precursor concentration is made adequate based
on a relationship between a film forming area and a precursor coating
amount. (Thus, it is not limited to 0.1 mol/l.)

[0154] This precursor solution is coated on the above-described patterned
SAM film using an inkjet method (see FIG. 7A). Using the inkjet method
liquid droplets are ejected not on the SAM film and only onto the
hydrophilic portion, so that a coating film was formed only on the
hydrophilic portion due to a contrast in the contact angle.

[0155] Using the continuous laser irradiating apparatus 71, a laser light
irradiation and heating were performed on the coating film, a solvent is
evaporated, obtaining a thermally decomposed coating film (see FIG. 7B).
Next, the thermally decomposed coating film was imaged by the imaging
unit 73, and an optimal laser power to be irradiated onto the thermally
decomposed coating film, from the imaged pattern image (see FIG. 7C).
Then, using the pulse laser irradiating apparatus 72, laser light
irradiation and heating were performed on the thermally decomposed
coating film only to crystallize the thermally decomposed coating film
(see FIG. 7D). At this time, an optimal laser power determined in FIG. 7C
were irradiated.

[0156] Here, as the thickness of the coating film coated on the patterned
SAM film by the inkjet method may be determined from a coating amount,
data on a laser power corresponding to a film thickness of coating film
that is recorded in advance are read, and the continuous laser
irradiating apparatus 71 and the pulse laser irradiating apparatus 72 are
operated with the read laser power (the laser light was successively
irradiated.)

[0157] Liquid droplets were ejected onto the same position by an inkjet
method, a process of performing laser light irradiation by the continuous
laser irradiating apparatus 71 and the pulse laser irradiating apparatus
72 were repeated 15 times to perform wet-on-wet coating to obtain an
electro-mechanical transducer film of 500 nm. No failures such as cracks,
etc., occurred for the electromechanical transducer film produced.

[0158] Liquid droplets were ejected onto the same position by an inkjet
method, a process of performing laser light irradiation by the continuous
laser irradiating apparatus 71 and the pulse laser irradiating apparatus
72 were further repeated 15 times (for a total of 30 times), but no
failures such as cracks, etc., occurred in the electromechanical
transducer film. The film thickness of the electromechanical transducer
film reached 1000 nm.

[0159] An upper electrode (platinum) film is formed onto the patterned
electro-mechanical transducer film to produce an electro-mechanical
transducer element to evaluate electrical characteristics and
electromechanical transducer performance (a piezoelectric constant). FIG.
17 is graph showing a P-E hysteresis curve of the electro-mechanical
transducer element manufactured in the present example. It was found
that, the electro-mechanical transducer film has equivalent properties as
normal sintered ceramics with a relative permittivity of 1220, a
dielectric loss of 0.02, a residual polarization of 19.3 μC/cm2,
and a coercive electric field of 36.5 kV/cm.

[0160] The electro-mechanical transducer performance of the
electro-mechanical transducer element was calculated by measuring a
deformation amount due to electric field application with a laser Doppler
vibrometer and calibrating by a simulation. The piezoelectric constant
d31 thereof became -20 pm/V, which also was equivalent to that of the
sintered ceramics. This is a characteristic value which may be adequately
designed as a liquid droplet ejecting head.

[0161] Oxides such as LaNiO3, SrRuO3, etc., and platinum may be
dissolved in a solvent, coating and laser irradiation are performed by an
inkjet method to also form an electrode film in the same manner as the
electro-mechanical transducer film.

[0162] While preferred embodiments and examples have been described in the
above in detail, they are not limited to the above-described embodiments
and examples, so that various changes and modifications may be added to
the above-described embodiments and examples without departing from a
scope recited in the claims.

[0163] The present application is based on Japanese Priority Application
No. 2011-286156 filed on Dec. 27, 2011, Japanese Priority Application No.
2011-286157 filed on Dec. 27, 2011, and Japanese Priority Application No.
2011-286158 filed on Dec. 27, 2011, the entire contents of which are
hereby incorporated by reference.

Patent applications by Masahiro Yagi, Kanagawa JP

Patent applications by Norbert Pirch, Aachen DE

Patent applications by Osamu Machida, Kanagawa JP

Patent applications by Ryo Tashiro, Kanagawa JP

Patent applications in class MEASURING, TESTING, OR INDICATING

Patent applications in all subclasses MEASURING, TESTING, OR INDICATING